Process of treating fruit



Oct. 16, 1945. A. F. KALMAR PROCESS OF TREATING FRUIT Filed March 22, 1943 V V ,Ev

against reinfection.

Patented Oct. 16, 1945 UNITED STATES PATENT OFFICE I 2,386,954 PnocEss or' 'raEA'rlNG FRUIT Y Arthur F. Kalmar, Riverside, Calif., assigner to Food Machinery Corporation, San "Jose, Calif., a corporation of Delaware Application March 22, 1943, Serial No. 480,007

9 Claims. (61.99-156) This invention has to do with the treatment of fruit and vegetables for the prevention of decay.

Although especially useful in the treatment of citrus fruit, it is likewise adaptable for treating a wide variety of fruits and vegetables, includin'g apples, tomatoes. and cantaloupes.

, It is a broad object of this invention to provide an improved process for treating fresh whole fruit when preparing thimfor market, to prevent decay thereof caused by blue and green mold during the considerable period of time which often elapses between the harvesting of the fruit and its ultimate consumption.

The decay of fresh fruit and vegetables, and particularly of Vcitrus fruit, results mainly from infection taking place in injuries received in the pickingA and handling of the fruit incidental-to its being harvested. To prevent this infection causing decay the fruit is generally disnfected shortly after it arrives at the packing house. To be suitable for this purpose, any .disinfecting agent must be applied so that it extends into the cuts and punctures present in the rind of the fruit.'

A This agent must also have no tendency to burn or injure vthe rind of the fruit.

Even though disinfeeted in this manner, the fruit is subject; to re-'infection by the introduction of mold spores ypresent in the air into the rind injurieswhich did not heal as a result of said disinfection. As considerable decay is often caused by this re-infection, efforts have been made to find a suitable agent which can be applied to the fruit so as to penetrate the injuries and remain active there so as to lkill any mold spores having access to these injuries. y

It is another object of my invention to provide a process of treating fruit in which the optimum causes aforestated, the practice generally followed in harvesting lemons prior to my invention has been to treat the lemons at the time they are washed, before placing them in storage, with a hot solution of soda ash. 'I'o prevent reinoculation of the fruit during its long storage, the soda ash solution was not rinsed from the fruit, so that the surface of the fruit was covered with a thin lm of soda ash when the solution dried. Sweating of the fruit in storage, which takes place not infrequently in California, produced a con-- centrated solution of soda ash on the rind of the fruit, which saponified the oils and waxes present on the rind. This was found to produce a substantial acceleration ofthe shrinkage rate of the fruit. Another difdculty with the soda ash treatment was the fact that it was an effective fungicide only when applied at a temperature of from 110 to 120 degrees Fahrenheit, and that to prevent the oleocellosis or green spotting ofthe lemons by the releasing of lemon oil from the rinds by the heat, it was necessary for the lemons to be temporarily stored on the iioor of the packy ing house from one to three days before treating agents and conditions are brought to bear upon the fruit for disinfecting the same, and the optimum agents andconditions are also broughtto bear upon the fruit for immunizing the same While applicable to other fruits and vegetables, the process of my invention is especially useful in the treatment of lemons, as it presents a solution to many problems met within the preparation of lemons for market, vand hitherto inadequately solved.

Lemons are picked according to size, and a large portion of these are green when picked and arestored for as much as several months to permit the fruit to ripen and acquire a natural lemon color before being packed for shipment. Some of the fruit when picked is, ofcourse, already ripe and yellow in color, but the greater portion is p process for treating lemons by which the lemons may be treated immediately upon their coming A into the packing house from the field, which will f j. fore these have an opportunitymf healing over,

' by the storage andlmarketing of the fruit, and

the lemons and placing them in the ripening stor.. age rooms. 'I'his extended delay between the picking and washing of the lemons caused a cer- ,tain portion of the rind wounds in the fruit to heal over, thereby trapping mold fungus therein, so that these wounds would not be. disinfected by the soda ash and would continue to infect and ultimately cause decay of the fruit.

v. It'is an object of my invention to provide a disinfect all the injuries in the lemon rind beand-which will immunize these injuries against re-infection. during succeeding periods taken up which will not increase the normal shrinkage rate of the lemons.

It is another object" `of my invention to provide Y a. process of treating lemons, as aforesaid, which will not only not increase the normal shrinkage -rate of lemons, but which can beemployed to soluble salts of hydroxy diphenyl. available salt of this class for this purpose is One 'class ^of-agents suggested as suitable for both disinfecting'citrus fruit and then immunizing it against subsequent re-infectionare water The most sodium' orthophenylphenate. (See U.'S. Letters Patent No. 2,054,392,- to J N. Sharma.) for this agent to be used for this dual purpose', the fruit must be submerged inasolution of the agent, or the solution flooded over the fruit so thata considerable body =of the solution mustbe prepared and used over and over again on the fruit. This agent has a tendency to hydrolyze when in a dilute solution, forming the insolublel use this agent for the initial disinfection of citrus fruit. whichunecessarily involves contacting the fruit over and over again with thesame body of solution, I find that the free alkali inthe solution reacts with C02 absorbed from the air, so that very close attention has to be paid to the solution to keep enough alkali therein to depress hydrolysis of the orthophenylphenate without getting so much alkali in the solution that the alkali itself will burn the fruit.

As will be pointed out hereinafterin describing my invention, I have discovered that sodium in connection with the use of a, hydrolysis depressant for the purposeof immunizing fruit from l re-iniecvtion;

I have also discovered, and it is an' object of my invention to provide, a, mode of ap- In order y asados-1 control'and reduce, as desired, said shrinkagel culture and Forestry, Division of Plant Industry, Union of South Africa, for the year June 1937 to June 1938, published 1939 by Government Printer, Pretoria.)

I have discovered that even though the hypochlorite be thoroughly rinsed from the fruit before applying sodium orthophenylphenate thereto, suiiicient quantities of hypochlorite are retained in the cuts and .punctures `in the rind of the fruit, which it is particularly necessary to immunize, and thai-,this hypochlorite has such a pH value, generally above l10, that any sodium orthophenylphenate which is thereafter applied without prohibitive delay will penetrate into the injuriesv and be converted into sodium chlororthophenylph'enate.

l It is another `object of my invention, therefore, to overcome this nullication of the orthophenylphenate and to provide a dual process of sterilizing and immunizing fruit, in which the` primary or sterilizing step is performed by a hypochlorite of an alkali forming metal, and th'e secondary or immunizing step is performed by a'water soluble salt of hydroxy diphenyl. By alkali forming metal, I Vmean those metals (like sodium and calcium) the dxides and hydroxides of which are commonly referred to as alkalies.

It isa further objectl of my invention to provide a process of treating fruit in which a water f orthphenylphenate may be practically applied plying this agent in combination with' other means for dislnfecting the fruit initially so as l to give a commercially practicable method which performs both functions of disinfecting the fruit and then immunizing it against re-infection. l The process -of my invention thusinvolves the use of a primary agent, the principal function and purpose of which is sterilization, and a secondary agent,the principal function and purpose of which is immunization.

` Among the more powerful disinfectants which have had wide use in the disinfecting of citrus fruit, is sodium hypochlorite. ent No. `1,842,696.) advantages derived from the fact that itoperates (See Slater Patat normal atmospherictemperatures, thus making it unnecessary to' heat-.the bath in which it is applied or to heat the fruit in processing it.

' Although a powerful fungicide and completely non-toxic to the fruit in customarily used concentrations, sodium hypochlorite cannot serve as an immunizer, as it breaks-A down within a relatively short time into products of reaction which are ineffective as fungicides. Moreover, sodium hypochlorite reacts with sodium orth'oplienylphenate, under the' pH conditions normally existing`in hypochlorite solutions applied to fruit, to

iorm, sodium chlororthophenylphenate a compOund which is much less potent against blue and green mold that eith'er'ofthe reactants. (See -Dip`ping experiments with oranges, by J. M.

This agent has enormous soluble salt of hydroxy diphenyl may be applied tothe fruit without the necessity for constantly watching the alkalinity of the solution to maintain herein a suitable quantity `of hydrolysis depressant.

Yet another object of my invention is to prothe subsequent scrubbing of the fruit withA brushes in a washing machine while the detergent 'solution vis flooded over the fruit. When the process oi' my invention is thus performed, the fruit is first treated with a. bathof a solution of sodium hypochlorite for a period of from four to five minutes, this solution being preferably at a'temperature of about 70 degrees Fahrenheit.

Although in some instances a lower strength of hypochlorite solution is desirable, this solution lwhen used on lemons and other citrus fruit, prefe'rably contains .3% to 3.% YhypochlorlteA by weight. -A wetting agentmay also be, and preferably is, added to this solution. so as `to assistin f loosening the scale `adhering to the fruit without the necessity of elevating the temperature of the latter,and to cause the" hypochlorite. to readilyx'wet all surfaces contacted thereby, includfound especially suitable for this purpose is sodi- 'um secondary tetradecyl sulfate which is commercially known as "TergitolNo. 4." A buffer to maintain the pH'between about 8.6

. vand 9.4 is also preferably added to the hypochlorite solution. )This increases the fungicidal activity of the hypochlorite. Suitablebuiers-for- 2,386,954 this purpose are borax or a mixture of disodiun'iI phosphate and sodium carbonate.

Th'e fruit is next delivered into the detergent washing solution in which I place a reducing agent which operates rapidly onany hypochlorite present on the fruit, to reduce this to a relatively inert compound. An agent suitable for this purpose may be selected from a group as follows:-

phosphitess sulphites, bisulphites, metabisulphites, and thiosulphates of alkali forming metals.

I have found sodium thiosulphate is especially of this function need not be more than 1.5% by weight.

Following this treatment in this combined solution of detergent and reducing agent, the fruit is delivered to a washer in `which is scrubbed by -brushes while having said detergent solution flooded thereover. f

The fruit is then rinsed by a spray of Afresh water, and delivered to a suitable conveyor.

While fruit is carried on this conveyor it is treated with a pressure spray of an vimmunizing solution. This solution contains a water soluble salt of hydroxy disphenyl, together with a hydrolysis depressant in quantity sumcient to maintain the pH valule of the solution preferably within a range of about 10.2 to 11.5. The immunizing agent preferably used in the solution is sodium orthophenylphenate, and the preferable quantity is from about .02% to abolut 1.5% by weight. 'I'he hydrolysis depressant used in this solution is preferably sodium hydroxide. The exactly correct amount of this depressant is maintained in this solution by making this solution up daily in an amount suitable for the days run, and then applying this solution to the fruit only once by the spray method, so that the solution is not aerated until it is sprayed onto the fruit. The fruit is then allowed to dry and the water thus evaporated from the immunizing solution, leaving crystals of sodium orthophenylphenate or a concentrated solution thereof, on the surface of the fruit and in the cuts and punctures in the' rind thereof, before an opportunity occurs for the hydrolysis-and conversion of this agent into its oil soluble, rind-burning form.

Hydrolysis of the sodium orthophenylphenate after it has'been applied in the process of my invention, cannot occur, as even though crystals .of this agent on the rind'of the fruit may be redissolved when the fruit sweats, the solution produced thereby is always a concentrated one,

whereas hydrolysis can take --place onlyl in a dilute solution.

The process of my invention is adaptedto be performed as aforestated, either in conjunction with a washingprocess or otherwise, and it may also include the application of an aqueous `wax emulsion commonly known as water wax" inthe solution of immunizing agent, so that the fruit is not only immunized, but a deposit of`wax made on the rind thereof to give a desired degree of reduction of theshrinkage of thefruit. This added'feature of my process is especially desirable when treating lemons produced. in areas where atmospheric conditions are such that otherwise considerable shrinkage would be caused Vduring the normal storage periods.

Specific formulas for the three solutions o process vwhich I'have found to give especially good results on fresh are as follows:

Disnfecting solution l Per cent by weight Sodium hypochlorite expressed as available chlorine .6

Buier, consisting of Disodium phosphate 1.25 Sodium carbonate 0.35 Wetting agent consisting of Tergitol No. 4- i 0.15 Water and inert sa1ts 97.65

Detergent consisting of- Solution of reduoing agent and detergent rerl cent by 'weight Soap V0.20 Sodium carbonate .50 Reducing agent-sodium thiosulphate 0.15 Water 99.15

Immunzng solution Per cent by weight Sodium .orthophenylphenate l 0.15

for water-waxing the fruit, are asfollws:

Per cent Paraiiin wax 2.0 Nopco #2251 (emulsifying agent) 0.5 Sodium `orthophenylphenate '0.15 Sodium hydroxide .02 Water 97.33

Y Per cent Paraflin wax. 1.5 Beeswax v 0.5 Triethanolamine oleate 'y A Sodium hydroxide .02 Sodium orthophenylphenate .15 Water 97.43

10o oo III.

. Per cent Parafiin vwax 1.0 Atlasy #2000 (emulsifying agent) r 0.2 Sodium orthophenylphenate .15 Sodium hydroxide .02 Water 98.63

100.00 In general, the ingredients of the immuniz- Hydrolysis depressantsodium hydroxide 0.02 Water 99.83

Typical formulas for thez immunizing solution of my process when this process is also employed The process of myl invention when performed whole lemons in California,`

'toren online a-Aof Fig. 2.

' trates an apparatus Il, which includes a solution tank il, having submerging rotors l2, a

delivery board il, over which fruit is delivered Y into the receiving end of the tank, and a discharge conveyor il for removing fruit'frm the opposite end ci' the tank. Fruit discharged from the latter conveyor travels overa delivery board il into a solution tank It having one or more submerging rotors'v I1, and a dischargel conveyor il. During the operation of the apparatus i0, the

rotors vi2 and I1 are slowly-rotated by a shaft Il in the direction indicated by the adjacent arrows.

'ranks u and It ere provided `wiin drains zn and 2l. Fruit discharged from the elevator il vtravels over a delivery board 25 onto rotating brushes 2l of a transverse fruit washer 21. A pump system 2l delivers solution from the tank :,ssacos which the hypochlorlte is introduced into all of Il to a series of notched troughs '23, overlying Lthe bnlshes 2l, so that the fruit resting on these brushes and brushed as the latter rotate, is

flooded with solution from the tank IG. as clearly shown in Figs. 2, 4 and 5. A drain pan 3|! returns this lsolution to the tank It.- The troughs 29 do not voverlie the final brushes 2i in the washer 21, and a fresh water supply pipe 35, extending overX the valley between the last two of these brushes, sprays fresh waterdownwardly on the fruit in Athis valley Ito rinse solution from this'fruit, the

rinsewater being collected ina drain pan 36 therebelow.

Whenfdischaig'ed from the washer 21 the fruit travelsover a drop board 31 onto 'a short upwa'rdlyA inclined roller conveyor 3l of an immunizer II. The rimmunizer l! is equipped with a solution tank M, from which a'pump 4i draws solution and delivers this under pressure to a pair of manifold supply pipesllinozzles 43 of which are staggered so as to thoroughly cover all of the fruit passingy therebeneath on the conveyor Il, with a relatively hard spray of solution from the tank `lli. Beneath the conveyor 38 is pro-v vided a drain pan 46. A' drain conduit I1 leads from the drain pans It and 46 to the sewer.

Whendischarged from the immunizer 39 the fruit may be received by any suitable piece of apparatus for handling the same, a sizer 43 being 'shown inthe drawing as located to receivethis fruit..

In employing the apparatus I0 to perform the process of my invention, the tank Il is provided withl a solution H, which is the hypochlorite solution of my invention; the'tank I6 is provided with a solution R, which is the detergentA and reducing agent solution of my invention, whilethe tank 40 is provided with a solution-O, which is the solution' of a water soluble salt of hydroxy diphenyl of myrinvention. This latter is, of

course, preferably sodium orthophenylphenate.

'immunizing agent. and preventing its being the cuts and punctures in the rind oftheirult. and the scale adhering to the rind surface is 'loosened up without any heating of the fruit. so

that the scale will readily be removed when the fruit reaches thewasher 21. Kt the 'completlon of this step, the yfruit is .delivered by the elevator i4 into the tank it. in wliionthe reducing agent in the solution R, attacks all traces of hypochlorite remaining on the fruit. and parf ticularly in. the punctures and cuts in the rind thereof. and reduces this hypochiorite to an inert form which will not combine with the orthophenylpl'lenate in solution O. -As the solution R is flooded over the fruittraveling through the Vwasher 21, ample opportunity is given in this cleansede by the scrubbing action of the brushes 2l thereon, and theaction of the detergents dissolved in the solution R. e v

The fruit then passes through .the sprays of clear water delivered by the manifold, which rinses practically all of the solution R from the surface of the fruit. The fruit is then delivered onto the conveyor 3l, where the solution ,O is applied thereto forcibly-by the pressure produced by the pump Ilf. This solution is only applied to the fruit once. and any'excess draining from the fruit ls'caught by the pan `v4I and discharged to the sewer by conduit pipe 4 1.

The solution O `iu tank 40 is protected from aeration in the atmosphere so. that the hydrolysis depressant therein remains throughout rthe day at a strength adequate to maintain,` the orthophenylphenate in the solution in its water soluble form, in which it is extremely effective as an i-,ransrormed` by hydrolysis into ite oil soluble form, which is toxic to the fruit. kWhen the process 0f my invention includes thel step of water-waxing the fruit, the immunizing and water-waxing occur simultaneously as the spray of solution O contacts the fruit traveling on the conveyor 3l.

. What I claim is:

l. A method of protecting fresh w ole fruit from decay which comprises: contacting the fruit with an aqueous-solution of a 'hypochlorite of an alkali forming metal, subsequently contacting said fruit with an aqueous solution containing a reducing agent selected from a group consisting of phosphites, sulphites, bisulphites, metabisulphites and thiosulphates of alkali forming metall and contacting said fruit with an aqueous solution containing awater soluble salt of hydroxy iiiphenyl.

2. A method of protecting fresh whole fruit from decay which comprises: contacting the It is believed clear from the previous desorip- 'tion of the process of my invention and of the apparatus i0, -how the latter functions in pel-` tforming this process. The `fruit delivered over '-75 with an aqueous solution of a hypochlorlte of an v fruit with an aqueous solution fof a hypochlorite of an'alkali forming metal, subsequently contacting said fruit with an aqueous solution containinga reducing agent selected from a group consisting ,of phosphites, sulphites, bisulphites, metabisuiphites and thiosulphates of alkali forming metals, and contacting said fruit with an aqueous solution containing a water soluble salt of hydroxy diphenyl and a hydrolysis depressant lsuilicient to maintainthe pH above 10.

j 3. A method of protecting fresh whole fruit l from Vdecay whichcomprises: contacting the fruit contacting said fruit with an aqueous medium vcontaining from about-.02% to about 1.5% by weight ot a water soluble salt of vhydroxy diphenyl and a hydrolysis depressant sufficient to maintain "the pH above 10.

4. A method of protecting fresh whole fruit from decay which comprises: contacting the fruit with an aqueous solution of sodium hypochlorite, subsequently contacting said fruit with an aqueous solution containing a reducing agent selected from a group consisting of phosphltes, sulphites, bisulphites, metabisulphites and thiosulphates of alkali forming metals and contacting said fruit with an aqueous medium containing from about .02% to about 1.5% 'by weight of sodium orthophenylphenate and a hydrolysis depressant sulcient to maintain the pH above 10.

5. A method of washing fresh whole fruit and protecting the same from decay which comprises: passing said fruit through a-n aqueous solution of a hypochlorite of an alkali forming metal; passing said fruit through an aqueous'solution of a detergent also containing a reducing agent selected from a group consistingof phosphites, sulphites, bisulphites, metabisulphites and thiosulphates of alkali forming metals; brushing said f fruit while in contact. with said solution of deter- A from decay which comprises: contacting the fruit with an aqueous solution of a hypochlorite of an water soluble salt of hydroxy diphenyl containing a waxy coating material suspended therein.

--7Q A method o'f protecting fresh whole fruit from decay which comprises: contactingl the fruit with an aqueous solution of a hypochlorite of an alkali forming metal; subsequently contacting said fruit with an aqueous medium containing a reducing agent selected from a group consisting of phosphltes, sulphites, bisulphitesfmetabisulphites and thiosulphates of alkali forming met als; rinsing said solution of reducing agent from said fruit; spraying onto said fruit an aqueous f solution containing a water` soluble salt of-hydroxy diphenyl; and permitting said solution sprayed onto said fruit to dry thereon.

8. A method of protecting fresh whole fruit /from decay which comprises: contacting the fruit with an aqueous solution of a hypochlorite of an alkali forming metal; subsequently contacting said fruit with` an'aqueous solution containing a. reducing agent selected from a group `consisting of phosphltes, sulphites, bisulphites, metabisulphites and thiosulphates of alkali forming metals; rinsing said fruit with fresh water; forming an aqueous solution containing a water soluble salt of hydroxy diphenyl and a' free alkali in sufficient quantity to maintain the pH above 10; confining said diphenyl solution to substantially prevent acalkali forming metal; subsequently contacting said fruit with an aqueous solution of'a reducing agent selected from a` group consisting of phosphites, sulphites, bisulphites, metabisulphites and thiosulphates of alkali forming metals; and contacting said fruit with an aqueous solution of a phenyl solution onto said fruit; and permitting said solution to dry on said fruit.

9. A method of protecting from decay fresh whole fruit having external injuries, said method comprising: contacting the outervsurface of the fruit with an aqueous solution of a hypochlorite ARTHUR F. KALMAR. 

